Surfactants based on monounsaturated fatty alcohol derivatives

ABSTRACT

Surfactant compositions comprising an alkoxylate, a sulfate, or ether sulfate of a C 10 -C 12  monounsaturated alcohol are disclosed. The alkoxylate, sulfate, or ether sulfate may derive from undecylenic acid or undecylenic alcohol. Compared with their saturated analogs, the monounsaturated alkoxylates, sulfates, and ether sulfates are less irritating, making them valuable for personal care, laundry, cleaners, and other household applications. Microscopy studies show that the alkoxylates, sulfates, and ether sulfates have favorable phase behavior over a wide range of actives levels, expanding opportunities for products with greater compaction. When combined with cationic surfactants, the alkoxylates, sulfates, and ether sulfates exhibit synergy, and they have improved solubility compared with their saturated analogs. The surfactants find value for the personal care, laundry and cleaning, emulsion polymerization, agricultural products, oilfield applications, and specialty foams industries.

FIELD OF THE INVENTION

The invention relates to surfactants, and in particular tomonounsaturated fatty alcohol derivatives useful therein.

BACKGROUND OF THE INVENTION

Fatty alcohol derivatives, particularly alkoxylates, sulfates, and ethersulfates, are versatile surfactants. They are used across a broad arrayof industries and end uses, including personal care, laundry andcleaning, emulsion polymerization, agricultural uses, oilfieldapplications, industrial compositions, and specialty foamers.

Fatty alcohols are usually made by reducing the corresponding fattyacids or esters, typically by catalytic hydrogenation. Often, thecatalyst includes zinc or copper and chromium. U.S. Pat. No. 5,672,781,for instance, uses a CuCrO₄ catalyst to hydrogenate methyl esters frompalm kernel oil, which has substantial unsaturation, to produce amixture of fatty alcohols comprising about 52 wt. % of oleyl alcohol, amonounsaturated fatty alcohol. For additional examples, see U.S. Pat.Nos. 2,865,968; 3,193,586; 4,804,790; 6,683,224; and 7,169,959.

The fatty acids or esters used to make fatty alcohols and theirderivatives are usually made by hydrolysis or transesterification oftriglycerides, which are typically animal or vegetable fats.Consequently, the fatty portion of the acid or ester will typically have6-22 carbons with a mixture of saturated and internally unsaturatedchains. Depending on source, the fatty acid or ester often has apreponderance of C₁₆ to C₂₂ component. For instance, methanolysis ofsoybean oil provides the saturated methyl esters of palmitic (C₁₆) andstearic (C₁₈) acids and the unsaturated methyl esters of oleic (C₁₈mono-unsaturated), linoleic (C₁₈ di-unsaturated), and α-linolenic (C₁₈tri-unsaturated) acids.

Among fatty alcohols with internal unsaturation, oleyl alcohol has beenused as a starting material to make ether sulfonates that havesurfactant properties (see, e.g., U.S. Pat. Nos. 7,427,588 and7,629,299).

Monounsaturated feedstocks having reduced chain length have potentialvalue for making surfactants, but the feeds have not been readilyavailable. Recent improvements in metathesis chemistry (see, e.g., J. C.Mol, Green Chem. 4 (2002) 5 and U.S. Pat. Appl. Publ. Nos. 2010/0145086,2011/0113679, and 2012/0071676) will soon make such reduced chainunsaturated feedstocks available, but alternatives are needed.

Undecylenic acid (10-undecenoic acid) is produced industrially alongwith heptaldehyde by pyrolyzing the ricinoleic acid in castor oil (seeU.S. Pat. No. 1,889,348; J. Chem. Ed. 29 (1952) 446; J. Sci. Ind. Res.13B (1954) 277; and J. Am. Oil Chem. Soc. 66 (1989) 938). It is usedprimarily to manufacture pharmaceuticals, fragrances, and cosmetics.

Undecylenic acid is easily reduced to undecylenic alcohol with hydridereducing agents (e.g., lithium aluminum hydride) or selectivehydrogenation catalysts (see, e.g., J. Am. Chem. Soc. 59 (1937) 1. It isknown to ethoxylate undecylenic alcohol for possible use in laundrydetergents (JP 10140195). Undecylenic alcohol ethoxylates have also beenstudied as principal components of self-assembled monolayers, which canmimic membrane structure and function (see, e.g., U.S. Pat. No.6,809,196 and J. Am. Chem. Soc. 113 (1991) 12).

Undecylenic alcohol has been converted to sodium 10-undecenyl sulfate,and this compound has been used as a monomer for making polymerizablesurfactants (see, e.g., Electrophoresis 25 (2004) 622; New J. Chem. 16(1992) 883; and Langmuir 9 (1993) 2949).

Sulfation of alcohols produces alcohol sulfates, which have an C—O—SO₃Xgroup, where X is typically an alkali metal or ammonium ion from asubsequent neutralization step. Sulfonation of unsaturated hydrocarbonsgives sulfonates, which have a C—SO₃X group. When an unsaturated alcoholis the starting material, the unsaturated sulfate can be produced undersome conditions (see, e.g., WO91/13057). With other reagents, alcoholsulfation and carbon-carbon double bond sulfonation may compete, withmost of the reaction product resulting from sulfation, although thenature of the sulfonated by-products is generally not well understood(see, e.g., U.S. Pat. No. 5,446,188). Because of the competing sidereactions, unsaturated alcohols are usually avoided when the goal is tomake an alcohol sulfate or ether sulfate.

In sum, despite the known value of longer-chain fatty alcohols andshorter-chain saturated fatty alcohols for making ethoxylates, sulfates,and ether sulfates for use as surfactants, it is less clear what valuethe surfactants would have if they were made using shorter-chainunsaturated (e.g., C₁₀-C₁₂) fatty alcohols. The availability ofundecylenic acid and undecylenic alcohol as feedstocks invites furtherinvestigation.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to a composition comprising waterand 1 to 99 wt. % of a surfactant. The surfactant comprises analkoxylate, a sulfate or an ether sulfate of a C₁₀-C₁₂ monounsaturatedalcohol. In particular aspects, the alkoxylate, sulfate, or ethersulfate derives from readily available undecylenic acid or undecylenicalcohol. In other aspects, the surfactant comprises 40 to 60 wt. % of amonounsaturated C₁₀-C₁₂ primary alcohol sulfate and 40 to 60 wt. % of asecondary hydroxyalkyl C₁₀-C₁₂ primary alcohol sulfate.

We found that alkoxylate, sulfate, and ether sulfate surfactants madefrom C₁₀-C₁₂ monounsaturated alcohols offer unexpected advantages.Compared with their saturated analogs, the monounsaturated alkoxylates,sulfates, and ether sulfates are less irritating, making them valuablefor personal care, laundry, cleaners, and other household applications.Additional advantages are apparent from microscopy studies, whichindicate that the monounsaturated alkoxylates, sulfates, and ethersulfates have favorable phase behavior over a wide range of activeslevels. This enables formulation of products with greater compaction,allowing formulators to ship more product and less water in a givencontainer. When combined with cationic surfactants, the alkoxylates,sulfates and ether sulfates exhibit considerable synergy, and they haveimproved solubility compared with their saturated analogs.

The surfactants will be useful in many applications and industries,including personal care, laundry and cleaning, emulsion polymerization,agricultural products, oilfield applications, and specialty foams.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the invention relates to a composition comprising waterand 1 to 99 wt. % of a surfactant. The surfactant comprises analkoxylate, a sulfate or an ether sulfate of a C₁₀-C₁₂ monounsaturatedalcohol. Preferably, the composition comprises 2 to 98 wt. % of thesurfactant. More preferably, the composition comprises 5 to 95 wt. % ofthe surfactant.

As used herein, “monounsaturated” refers to compositions that compriseprincipally species having a single carbon-carbon double bond but mayalso include a minor proportion of one or more species that have two ormore carbon-carbon double bonds. The skilled person will appreciate thatit is not necessary and may be impractical to produce a purely“monounsaturated” species, and that mixtures comprising principally (butnot exclusively) monounsaturated alcohols and their alkoxylate, sulfate,and ether sulfate derivatives are contemplated as within the scope ofthe invention.

The alkoxylates, sulfates, and ether sulfates derive from a C₁₀-C₁₂monounsaturated alcohol. The unsaturation can be terminal or internal.Preferably, the alcohol is a primary alcohol. Thus, suitable C₁₀monounsaturated alcohols include 9-decen-1-ol, 8-decen-1-ol,7-decen-1-ol, 6-decen-1-ol, 5-decen-1-ol, 4-decen-1-ol, and3-decen-1-ol. Suitable C₁₁ monounsaturated alcohols include10-undecen-1-ol, 9-undecen-1-ol, 8-undecen-1-ol, 7-undecen-1-ol,6-undecen-1-ol, 5-undecen-1-ol, 4-undecen-1-ol, and 3-undecen-1-ol.Suitable C₁₂ monounsaturated alcohols include 11-dodecen-1-ol,10-dodecen-1-ol, 9-dodecen-1-ol, 8-dodecen-1-ol, 7-dodecen-1-ol,6-dodecen-1-ol, 5-dodecen-1-ol, 4-dodecen-1-ol, and 3-dodecen-1-ol.

Other surfactant components may be present in addition to thealkoxylate, sulfate, or ether sulfate of the C₁₀-C₁₂ monounsaturatedalcohol. Preferably, however, the surfactant comprises at least 10 wt.%, more preferably at least 20 wt. %, and most preferably at least 50wt. %, of the alkoxylate, sulfate, or ether sulfate of the C₁₀-C₁₂monounsaturated alcohol.

Undecylenic acid, because of its ready availability, is a preferredstarting material for making many of the unsaturated alcohols,particularly undecylenic alcohol. Reduction of the acid or its esterderivatives using catalytic hydrogenation (see J. Am. Chem. Soc. 59(1937) 1) or hydride reducing agents such as lithium aluminum hydride orthe like provides undecylenic alcohol (10-undecen-1-ol).

Other C₁₁ monounsaturated alcohols having an internal carbon-carbondouble bond can be made by isomerizing undecylenic alcohol tomore-substituted olefins, typically using a base catalyst (see, e.g.,Synthesis (1969) 97). Isomerization normally affords a mixture ofmonounsaturated alcohols, which may be desirable from a cost and/orperformance perspective.

When C₁₀-C₁₂ monounsaturated alcohols having the carbon-carbon doublebond in a particular location are needed, the Wittig reaction (see,e.g., Angew. Chem., Int. Ed. Engl. 4 (1965) 830; Tetrahedron Lett. 26(1985) 307; and U.S. Pat. No. 4,642,364) can be used. The choice ofstarting materials for the Wittig reaction will depend on availabilityof starting materials. In one approach, an w-hydroxyaldehyde and aphosphonium ylide (from the reaction of an alkyl halide andtriphenylphosphine to give a phosphonium salt, followed by deprotonationto give the ylide) are used:

In another approach, an aldehyde and a phophonium ylide prepared from anw-hydroxy alkyl halide are used:

4-Hydroxybutanal, which is produced in the manufacture of1,4-butanediol, can be reacted with the phosphonium ylide reagent from aC₆, C₇, or C₈ alkyl halide to make, respectively, 4-decen-1-ol,4-undecen-1-ol, or 4-dodecen-1-ol.

The Wittig reaction can also be used to produce terminally unsaturatedalcohols, e.g., with reagents such as triphenylphosphonium methylide. Insome cases, however, it may be more desirable to generate terminallyunsaturated alcohols in another way. For instance, reaction of anα,ω-diol with a suitable dehydrating agent (e.g., Ba₂P₂O₇, HMPA, or evena fatty acid) can provide good yields of terminally unsaturated alcohols(see, e.g., J. Org. Chem. 36 (1971) 3826 and U.S. Pat. Nos. 4,250,343;4,288,642; 4,447,659; 4,695,661, and 5,981,812, the teachings of whichare incorporated herein by reference).

Ester precursors to terminally unsaturated alcohols are also availablefrom metathesis chemistry. As an example, cross-metathesis ofunsaturated fatty esters with ethylene can be used to generateterminally unsaturated C₁₀-C₁₂ unsaturated esters. Reduction of theesters provides the terminally unsaturated C₁₀-C₁₂ alcohol. Forinstance, cross-metathesis of methyl oleate and ethylene provides1-decene and methyl 9-decenoate. The ester can be reduced to9-decen-1-ol (see, e.g., U.S. Pat. No. 4,545,941, the teachings of whichare incorporated by reference, and references cited therein). See alsoJ. Org. Chem. 46 (1981) 1821; J. Catal. 30 (1973) 118; Appl. Catal. 70(1991) 295; Organometallics 13 (1994) 635; Olefin Metathesis andMetathesis Polymerization by Ivin and Mol (1997), and Chem. & Eng. News80(51), Dec. 23, 2002, p. 29, which also disclose useful metathesiscatalysts.

In other aspects, undecylenic acid is used for the production of a C₁₀monounsaturated alcohol. In one approach, the terminal carbon-carbondouble bond is ozonized to give an aldehyde in which the chain length isreduced by one carbon. Reduction to a diol, followed by dehydration asdescribed above provides 9-decen-1-ol.

In other aspects, undecylenic acid is used for the production of a C₁₂monounsaturated alcohol. In one approach, the carboxylic acid group ishomologated (see, e.g., J. Org. Chem. 66 (2001) 5606 and TetrahedronLett. 21 (1980) 4461; 42 (2001) 7099), and the resulting unsaturatedcarboxylic acid is reduced to give 11-dodecen-1-ol. In another approach,undecylenic alcohol is hydroformylated, and the resulting aldehyde (oraldehyde mixture) is hydrogenated to give a diol. The diol is thendehydrated to give 11-dodecen-1-ol as the major product.

In other aspects, the monounsaturated alcohol or alcohol precursor(e.g., a fatty acid or ester) is generated using a microorganism orbioengineered microorganism, such as an algae, bacterium, or yeast-basedmicrobe.

Reduction of monounsaturated ester or acid precursors to produce theC₁₀-C₁₂ monounsaturated alcohols is performed using well-known catalystsand procedures. The reducing agent is typically either a hydridereducing agent (sodium borohydride, lithium aluminum hydride, or thelike) or molecular hydrogen in combination with a metal catalyst,frequently copper and/or zinc in combination with chromium (see, e.g.,U.S. Pat. Nos. 2,865,968; 3,193,586; 4,804,790; 5,124,491; 5,672,781;6,683,224; 7,169,959 and 7,208,643, the teachings of which areincorporated herein by reference).

The skilled person will appreciate that the reduction process,particularly when transition metal catalysts are used to convertprecursors to alcohols, can induce some degree of isomerization ormigration of the carbon-carbon double bond from its original position.Moreover, because hydrogenation catalysts are not always completelyselective, a proportion of the carbon-carbon double bonds might behydrogenated during the ester or acid reduction, resulting in a mixedproduct that may have saturated C₁₀-C₁₂ fatty alcohols in addition tothe desired unsaturated C₁₀-C₁₂ fatty alcohols. The skilled person cancontrol the degree of unsaturation to any desired amount.

The skilled person will, of course, recognize other desirable ways toarrive at the C₁₀-C₁₂ monounsaturated alcohols used to produce theinventive alkoxylate, sulfate, and ether sulfate-based compositions.

Monounsaturation can also impart advantages to formulated products(including consumer products) that are often not available with thecorresponding saturated fatty alcohol derivatives. Because crystallinityis disrupted by the presence of a carbon-carbon double bond,monounsaturated alkoxylates, sulfates, and ether sulfates usually havelower viscosities than their saturated analogs. Moreover, themonounsaturated alkoxylates, sulfates, and ether sulfates can beconcentrated and formulated at higher actives levels—sometimes muchhigher—than their saturated counterparts. For instance, a saturatedether sulfate might allow a maximum 30 wt. % actives level to give aflowable liquid, whereas an otherwise similar monounsaturated ethersulfate could allow the actives level to be as high as 70 or 80 wt. %.Thus, the seemingly minor structural change to a monounsaturated productcan enable shipment of more concentrated products, reduce or eliminatethe need for special handling equipment, and/or ultimately providesubstantial cost savings. The monounsaturated alkoxylates, sulfates, andether sulfates are also more effective as compatibilizers forsurfactants or other components in the fully formulated products.

The inventive alkoxyaltes, sulfates, or ether sulfates are made byalkoxylating, sulfating, or alkoxylating (preferably ethoxylating) andsulfating the monounsaturated C₁₀-C₁₂ alcohol compositions usingwell-known techniques.

For instance, the unsaturated C₁₀-C₁₂ alcohol can be alkoxylated byreacting it with ethylene oxide, propylene oxide, or a combinationthereof to produce an alkoxylate. Alkoxylations are usually catalyzed bya base (e.g., KOH), but other catalysts such as double metal cyanidecomplexes (see, e.g., U.S. Pat. No. 5,482,908) can also be used. Theoxyalkylene units can be incorporated randomly or in blocks. A series ofproducts with different degrees of alkoxylation can be easily producedusing a single reactor. This is illustrated in the examples below in thesequential ethoxylation of undecylenic alcohol to produce ethoxylateshaving, on average, 1, 3, or 7 moles of oxyethylene units per mole ofunsaturated C₁₀-C₁₂ alcohol starter.

The unsaturated C₁₀-C₁₂ alcohol can be sulfated, with or without a prioralkoxylation, and if applicable, neutralized to give a monounsaturatedalkyl sulfate or a monounsaturated alkyl ether sulfate according toknown methods (see, e.g., U.S. Pat. No. 3,544,613, the teachings ofwhich are incorporated herein by reference). Sulfamic acid is aconvenient reagent that sulfates the hydroxyl group without disturbingthe unsaturation. Thus, warming the monounsaturated alcohol oralkoxylate with sulfamic acid optionally in the presence of urea oranother proton acceptor conveniently provides the desired C₁₀-C₁₂monounsaturated alkyl ammonium sulfate or ether sulfate (see examplesbelow). The ammonium sulfate is easily converted to an alkali metalsulfate by reaction with an alkali metal hydroxide or other ion-exchangereagents. In the examples below, monounsaturated alkyl sodium sulfatesare prepared from the corresponding ammonium sulfates by reacting thelatter with aqueous sodium hydroxide.

Other reagents can be used to convert hydroxyl groups of a C₁₀-C₁₂unsaturated alcohol or alkoxylate to sulfates. For instance, sulfurtrioxide, oleum, or chlorosulfonic acid may be used. Some of thesereagents can, under the right conditions, also react with theunsaturation to form a sulfonate (having a carbon-sulfur bond), whichmay or may not be the desired outcome. Sulfur trioxide, for instance,can be used to sulfate the hydroxyl group of an unsaturated alcohol oralkoxylate, but it may also react with a carbon-carbon double bond togenerate a β-sultone, which can ring open to give mixtures ofhydroxyalkane sulfonates and alkene sulfonates. Thus, it is possible,and may be desirable, to perform both sulfation and sulfonation in onepot, and often with a single reagent. A product having at least someproportion of material that is both sulfonated and sulfated might bedesirable. For instance, a combined sulfate/sulfonate can impartbeneficial properties to the bulk surfactant, including reducedviscosity, better concentratability, better compatibilizing properties,or other advantages.

The invention includes processes for making alkoxylates, sulfates, andether sulfates of C₁₀-C₁₂ monounsaturated alcohols. The processescomprise reacting a composition comprising a C₁₀-C₁₂ monounsaturatedalcohol with an alkoxylating agent, a sulfating agent, or analkoxylating agent followed by a sulfating agent, to make, respectively,an alkoxylate, a sulfate, or an ether sulfate. Thus, one suitableprocess comprises sulfating the monounsaturated C₁₀-C₁₂ alcoholcomposition to give an alkyl sulfate. Another suitable process comprisesalkoxylating the C₁₀-C₁₂ alcohol composition with one or more alkyleneoxides, preferably ethylene oxide, to give a monounsaturated alkoxylate,followed by sulfation to give a monounsaturated alkyl ether sulfate.

As discussed earlier, the inventive surfactant compositions comprisewater and 1 to 99 wt. % of a surfactant comprising an alkoxylate, asulfate, or an ether sulfate of a C₁₀-C₁₂ monounsaturated alcohol. Inone aspect, the surfactant comprises: (a) 40 to 60 wt. % of amonounsaturated C₁₀-C₁₂ primary alcohol sulfate; and (b) 40 to 60 wt. %of a secondary hydroxyalkyl C₁₀-C₁₂ primary alcohol sulfate. Preferably,the surfactant comprises 45 to 55 wt. % of the monounsaturated C₁₀-C₁₂primary alcohol sulfate; and 45 to 55 wt. % of the secondaryhydroxyalkyl C₁₀-C₁₂ primary alcohol sulfate. The sulfate compositionmay further comprise 0.1 to 20 wt. %, preferably 0.5 to 15 wt. %, ofsulfonated products.

Although sulfation and sulfonation are known to compete when anunsaturated fatty alcohol is the starting material, we surprisinglyfound that certain sulfation conditions, such as falling-film sulfationusing sulfur trioxide, can provide roughly equal amounts of (a) amonounsaturated C₁₀-C₁₂ primary alcohol sulfate and (b) a secondaryhydroxyalkyl C₁₀-C₁₂ primary alcohol sulfate. Without wishing to bebound to any particular theory, we believe that the products may resultfrom formation of an intermediate dialkylsulfate. Upon neutralization ofthe acid, the dialkylsulfate may undergo both elimination, to revertback to the unsaturated C₁₀-C₁₂ alcohol sulfate, as well as hydrolysisto afford the hydroxyalkyl alcohol sulfate (see scheme below). Thehydrolysis appears to be selective, providing preferentially thesecondary alcohol and the primary alcohol sulfate. Consequently, theproduct mixture from reaction of a C₁₀-C₁₂ monounsaturated alcohol,particularly one that is not ethoxylated, typically comprises about 90%sulfates—with roughly equal amounts of monounsaturated C₁₀-C₁₂ primaryalcohol sulfate and C₁₀-C₁₂ secondary hydroxyalkyl alcohol sulfate—andabout 10% sulfonated products. As illustrated for a C₁₂ monounsaturatedalcohol:

In contrast, when ethoxylated C₁₀-C₁₂ alcohols are subjected tofalling-film sulfation with sulfur trioxide, the unsaturated ethersulfate predominates. For instance, an ethoxylate from 1 mole of EOgives about 70% unsaturated ether sulfate, and a 3 mole ethoxylate givesabout 80% unsaturated ether sulfate (see examples below).

In a preferred aspect, the monounsaturated C₁₀-C₁₂ primary alcoholsulfate and the secondary hydroxyalkyl C₁₀-C₁₂ primary alcohol sulfatederive from undecylenic alcohol.

In some preferred compositions, the monounsaturated C₁₀-C₁₂ primaryalcohol sulfate has the structure:R—O—SO₃Xwherein R is a linear or branched C₁₀-C₁₂ monounsaturated hydrocarbylgroup, and X is a mono- or divalent cation or an ammonium or substitutedammonium cation. Preferably, R is a linear C₁₀-C₁₂ monounsaturatedhydrocarbyl group.

We found that falling-film sulfation with sulfur trioxide tends toscramble carbon-carbon double bond geometry. Thus, the product mixturefrequently approaches a thermodynamically preferred mixture of cis- andtrans-isomers, usually about 8:2 trans-/cis-, even if the unsaturationin the unsaturated C₁₀-C₁₂ alcohol was predominantly or exclusively cis-or trans-.

In other preferred aspects, the secondary hydroxyalkyl C₁₀-C₁₂ primaryalcohol sulfate has the structure:CH₃—(CH₂)_(y)—CHOH—(CH₂)_(z)—O—SO₃Xwherein y=0 to 8, z=0 to 8, y+z=8 to 10, and X is a mono- or divalentcation or an ammonium or substituted ammonium cation. Preferably, y+z=9.

The sulfate compositions are preferably made by sulfating amonounsaturated C₁₀-C₁₂ alcohol with sulfur trioxide in a falling-filmreactor, followed by neutralization, according to methods describedearlier.

We also found that terminal unsaturation is not retained when sulfurtrioxide is used to make monounsaturated C₁₀-C₁₂ alcohol sulfates andether sulfates. Instead, isomerization occurs to give more-substitutedunsaturated products. Thus, in one inventive process, an internallymonounsaturated C₁₀-C₁₂ alcohol sulfate or ether sulfate is made. Thisprocess comprises reacting a terminally monounsaturated C₁₀-C₁₂ alcoholor alkoxylate with sulfur trioxide in a falling-film reactor, followedby neutralization.

We also observed positional isomerization upon sulfation of internallyunsaturated C₁₀-C₁₂ alcohols. This may occur through the regeneration ofan olefin when a dialkylsulfate eliminates in the “opposite” direction(or side of the chain) from which the addition had occurred. Whether ornot the olefin can fully “zip” up and down the chain is unclear.Positional isomerization could occur by multiple addition/elimination,olefin migration prior to addition of the sulfuric acid ester, or someother mechanism.

The alkoxylate, sulfate, or ether sulfate-based surfactant compositionsmay be incorporated into various formulations and used as emulsifiers,skin feel agents, film formers, rheological modifiers, solvents, releaseagents, biocides, biocide potentiators, conditioners, dispersants,hydrotropes, or the like. Such formulations may be used in end-useapplications including, among others: personal care; household,industrial, and institutional cleaning products; oilfield applications;enhanced oil recovery; gypsum foamers; coatings, adhesives and sealants;and agricultural formulations.

Thus, the alkoxylates, sulfates, or ether sulfates may be used in suchpersonal care applications as bar soaps, bubble baths, liquid cleansingproducts, conditioning bars, oral care products, shampoos, body washes,facial cleansers, hand soaps/washes, shower gels, wipes, baby cleansingproducts, creams/lotions, hair treatment products, antiperspirants, anddeodorants.

Cleaning applications include, among others, household cleaners,degreasers, sanitizers and disinfectants, liquid and powdered laundrydetergents, heavy duty liquid detergents, light-duty liquid detergents,hard and soft surface cleaners for household, autodish detergents, rinseaids, laundry additives, carpet cleaners, spot treatments, softergents,liquid and sheet fabric softeners, industrial and institutional cleanersand degreasers, oven cleaners, car washes, transportation cleaners,drain cleaners, industrial cleaners, foamers, defoamers, institutionalcleaners, janitorial cleaners, glass cleaners, graffiti removers,concrete cleaners, metal/machine parts cleaners, and food servicecleaners.

In specialty foam applications (firefighting, gypsum, concrete, cementwallboard), the alkoxylates, sulfates, or ether sulfates function asfoamers, wetting agents, and foam control agents.

In paints and coatings, the alkoxylates, sulfates, or ether sulfates areused as solvents, coalescing agents, or additives for emulsionpolymerization.

In oilfield applications, the alkoxylates, sulfates or ether sulfatescan be used for oil and gas transport, production, stimulation, enhancedoil recovery, and as components of drilling fluids.

In agricultural applications, the alkoxylates, sulfates, or ethersulfates are used as solvents, dispersants, surfactants, emulsifiers,wetting agents, formulation inerts, or adjuvants.

As demonstrated in the examples below, the inventive alkoxylate,sulfate, or ether sulfate-based compositions are exceptionally useful inapplications requiring low irritation, agricultural dispersants,water-soluble herbicides, aqueous hard surface cleaner degreasers andglass cleaners, and surfactant applications that require high activeslevels or improved solubility.

Preparation of Sulfates and Ether Sulfates from Undecylenic Alcohol

Undecylenic Alcohol Sulfate, Sodium Salt

A large-scale, water-jacketed (40° C.) batch reactor equipped withaddition funnel, mechanical stirring, and nitrogen inlet (5 mL/min. flowrate) is charged with undecylenic alcohol (125.5 g, 0.737 mol). Sulfurtrioxide (70.7 g, 1.2 eq.) is charged to the addition funnel, then addedcarefully to the vaporizer while maintaining the reaction temperaturebelow 50° C. Initial fuming in the headspace is severe. Following theSO₃ addition, the reactor is purged with nitrogen for 5 min. Totaladdition time: 2 h, 15 min. The acid intermediate is dark brown withmoderate viscosity.

A round-bottom flask equipped with mechanical stirring is charged withwater (418.4 g) and sodium hydroxide solution (61.6 g of 50% aq. NaOH).The acid intermediate from above (160.0 g) is added to the aqueous basesolution, and the resulting mixture is heated to and held at 70° C. for1 h. The product is filtered to remove particulates. ¹H NMR analysisshows migration of the carbon-carbon double bond and about 44% ofmonounsaturated C₁₁ primary alcohol sulfate. Solids: 28.1%; unsulfatedalcohol: 0.46%; inorganic sulfate: 0.24%; actives: 27.4%. Yield: 167.4 g(91%).

1-Undecanol Sulfate, Sodium Salt

The procedure described above is followed to prepare the saturated C₁₁alcohol sulfate from 1-undecanol (125.1 g) and sulfur trioxide (71.9 g,1.2 eq.). Total addition time for the sulfur trioxide: 1.5 h. The acidis dark brown with low viscosity.

Conversion to the sodium sulfate is performed using water (471.3 g),sodium hydroxide solution (68.7 g of 50% aq. NaOH), and the acidintermediate (180.0 g). The acid is added while keeping the reactiontemperature below 50° C., and the resulting product is mixed for 1 h.The pH is adjusted to 8.6 with 10% aq. H₂SO₄ solution, and the productis transferred to a jar. Solids: 24.9%; unsulfated alcohol: 1.27%;inorganic sulfate: 2.45%; actives: 21.2%. Yield: 190 g (100%).

Ethoxylation of Undecylenic Alcohol to Produce 1, 3, and 7 Mole AlcoholEthoxylates

Ethoxylations are performed sequentially using one reactor to prepareundecylenic alcohol ethoxylates that have, on average, 1, 3, or 7oxyethylene units.

Undecylenic alcohol (1796 g) is charged to a pressure reactor. LiquidKOH (45%, 17.6 g) is added. The reactor is sealed and heated to 100° C.under nitrogen with agitation. At ˜50° C., vacuum (20 mm) is applied toremove water. The contents are further heated to 105-115° C. undervacuum (20 mm) and held for 3 h with a nitrogen sparge.

The remaining dried catalyzed alcohol feed (1802 g) is heated to 145° C.The reactor is pressurized with nitrogen and vented three times.Ethylene oxide (460 g, 1 mole per mole of starter) is introduced to thereactor at 145-160° C. over 1 h. After the EO addition, the mixturedigests for 1 h at 150-160° C. until the reactor pressure equilibrates.The mixture is cooled to 50° C. and partially drained (380 g removed) toprovide the 1 mole ethoxylated unsaturated alcohol. Hydroxyl value: 259mg KOH/g; iodine value: 149 g I₂/100 g sample.

The reactor contents (1880 g) are re-heated to 145° C., and the reactoris vented with nitrogen as described earlier. Ethylene oxide (775 g, 2additional moles per mole of starter; 3 moles of EO per mole ofundecylenic alcohol charged) is added to the feed at 145-160° C. Afterdigesting 1 h at 150-160° C., the mixture is cooled to 60° C. andpartially drained (470 g removed) to recover the 3 mole ethoxylatedunsaturated alcohol. Hydroxyl value: 183 mg KOH/g; iodine value: 149 gI₂/100 g sample.

The reactor contents (2185 g) are re-heated to 145° C., and the reactoris vented with nitrogen as described earlier. Ethylene oxide (1265 g, 4additional moles per mole of starter; 7 moles of EO per mole ofundecylenic alcohol charged) is added to the feed at 145-160° C. Afterdigesting 1 h at 150-160° C., the mixture is cooled to 60° C. anddrained to recover the 7 mole ethoxylated unsaturated alcohol. Hydroxylvalue: 116 mg KOH/g; iodine value: 52 g I₂/100 g sample. Yield: 3450 g.

Ethoxylation of 1-Undecanol to Produce 1, 3, and 7 Mole AlcoholEthoxylates

Ethoxylations are performed sequentially using one reactor to prepare1-undecanol ethoxylates that have, on average, 1, 3, or 7 oxyethyleneunits.

1-Undecanol (1715 g) is charged to a pressure reactor. Liquid KOH (45%,18.0 g) is added. The reactor is sealed and heated to 100° C. undernitrogen with agitation. At ˜50° C., vacuum (20 mm) is applied to removewater. The contents are further heated to 105-115° C. under vacuum (20mm) and held for 3 h with a nitrogen sparge.

The remaining dried catalyzed alcohol feed (1713 g) is heated to 145° C.The reactor is pressurized with nitrogen and vented three times.Ethylene oxide (440 g, 1 mole per mole of starter) is introduced to thereactor at 145-160° C. over 1 h. After the EO addition, the mixturedigests for 1 h at 150-160° C. until the reactor pressure equilibrates.The mixture is cooled to 50° C. and partially drained (299 g removed) toprovide the 1 mole ethoxylated saturated alcohol. Hydroxyl value: 257 mgKOH/g.

The reactor contents (1854 g) are re-heated to 145° C., and the reactoris vented with nitrogen as described earlier. Ethylene oxide (750 g, 2additional moles per mole of starter; 3 moles of EO per mole of1-undecanol charged) is added to the feed at 145-160° C. After digesting1 h at 150-160° C., the mixture is cooled to 60° C. and partiallydrained (407 g removed) to recover the 3 mole ethoxylated saturatedalcohol. Hydroxyl value: 184 mg KOH/g.

The reactor contents (2197 g) are re-heated to 145° C., and the reactoris vented with nitrogen as described earlier. Ethylene oxide (1275 g, 4additional moles per mole of starter; 7 moles of EO per mole of1-undecanol charged) is added to the feed at 145-160° C. After digesting1 h at 150-160° C., the mixture is cooled to 60° C. and drained torecover the 7 mole ethoxylated saturated alcohol. Hydroxyl value: 116 mgKOH/g. Yield: 3472 g.

Preparation of Ether Sulfates

Undecylenic Alcohol, 1 EO Ether Sulfate, Sodium Salt

The procedure used for undecylenic alcohol is generally followed usingundecylenic alcohol 1EO ethoxylate (123.5 g, 0.578 mol) and sulfurtrioxide (55.5 g, 0.693 mol, 1.2 eq.). Total addition time: 1 h, 50 min.The acid intermediate (155.0 g) is combined with water (414.3 g) andaqueous sodium hydroxide solution (50.7 g of 50% NaOH) and heated 1 h at70° C. ¹H NMR analysis indicates 57% internal olefin and 13% terminalolefin present. Solids: 28.0%; unsulfated alcohol: 0.97%; inorganicsulfate: 0.14%; actives: 26.9%. Yield: 162.0 g (95%).

1-Undecanol, 1EO Ether Sulfate, Sodium Salt

The procedure used for undecylenic alcohol is generally followed using1-undecanol 1EO ethoxylate (123.2 g, 0.564 mol) and sulfur trioxide(53.9 g, 0.674 mol, 1.2 eq.). Total addition time: 1 h, 35 min. The acidintermediate (160.0 g) is combined with water (428.5 g) and aqueoussodium hydroxide solution (51.5 g of 50% NaOH) and heated 1 h at 70° C.Solids: 27.4%; unsulfated alcohol: 0.76%; inorganic sulfate: 0.52%;actives: 26.2%. Yield: 165.4 g (98%).

Undecylenic Alcohol, 3EO Ether Sulfate, Sodium Salt

The procedure used for undecylenic alcohol is generally followed usingundecylenic alcohol 3EO ethoxylate (118.9 g, 0.393 mol) and sulfurtrioxide (37.6 g, 0.469 mol, 1.2 eq.). Total addition time: 1 h, 30 min.The acid intermediate (140.0 g) is combined with water (384.8 g) andaqueous sodium hydroxide solution (35.2 g of 50% NaOH) and heated 1 h at70° C. ¹H NMR analysis indicates 62% terminal olefin and 19% internalolefin present. Solids: 27.2%; unsulfated alcohol: 1.61%; inorganicsulfate: 0.13%; actives: 25.4%. Yield: 145.1 g (97%).

1-Undecanol, 3EO Ether Sulfate, Sodium Salt

The procedure used for undecylenic alcohol is generally followed using1-undecanol 3EO ethoxylate (150.2 g, 0.493 mol) and sulfur trioxide(47.3 g, 0.591 mol, 1.2 eq.). Total addition time: 1 h, 25 min. The acidintermediate (180.0 g) is combined with water (495.1 g) and aqueoussodium hydroxide solution (44.9 g of 50% NaOH) and heated 1 h at 70° C.Solids: 26.8%; unsulfated alcohol: 1.09%; inorganic sulfate: 0.27%;actives: 25.5%. Yield: 186.4 g (98%).

Undecylenic Alcohol, 1 EO Ether Sulfate, Ammonium Salt

A four-neck flask equipped with overhead mechanical stirrer, condenser,nitrogen inlet, thermocouple, heating mantle, and temperature controlleris charged with undecylenic alcohol 1EO ethoxylate (111 g, 0.520 mol)and 1,4-dioxane (250 mL). Sulfamic acid (53.0 g, 0.546 mol) and urea(1.64 g) are added. The mixture is heated to reflux (about 103° C.) for4 h. Analysis by ¹H NMR (MeOD) indicates ˜99% conversion to sulfate.Upon cooling, the mixture becomes a slurry. Chloroform (500 mL) is addedand the mixture is heated to 55° C. Upon cooling and standing overnight,very fine insolubles settle to bottom. The solution is vacuum filteredusing filter aid and a coarse funnel, washing with fresh chloroform. Thefiltrate is concentrated by rotary evaporation. The dioxane-wet paste isthen dissolved in methanol (500 mL), adjusted to ˜pH 7 with ammoniumhydroxide, and then reconcentrated. This procedure is repeated 5X, withthe last concentration stopped before the product becomes too thick.Material is transferred to glass baking dish, using MeOH toquantitatively transfer residue. The solids are allowed to dry in a hoodover the weekend and then further dried in a vacuum oven (70° C., 5 h).The product is a yellow semi-solid. ¹H NMR analysis indicates 99%conversion to the ammonium sulfate.

1-Undecanol, 1 EO Ether Sulfate, Ammonium Salt

The procedure used above to convert undecylenic alcohol 1 EO ethoxylateto the ammonium sulfate is generally followed using 1-undecanol 1EOethoxylate (109.5 g, 0.508 mol), sulfamic acid (51.8 g, 0.533 mol),1,4-dioxane (250 mL), and urea (1.61 g). The product is a yellowsemi-solid. ¹H NMR analysis indicates quantitative conversion to theammonium sulfate.

Evaluation of Alcohol Sulfates and Ether Sulfates in Product DevelopmentApplications

Zein Test

The zein test is based on solubilization by surfactants of a yellow corn(maize) protein that is normally insoluble in water unless it isdenatured. The test gravimetrically determines the amount of zeindissolved by a surfactant solution. The solubility of zein in surfactantsolutions correlates well with skin irritation or roughness caused bythe surfactant. The “zein number” is a value relative to a normalizedcontrol, i.e., a 1% actives solution of Stepanol® WA-Extra PCK (sodiumlauryl sulfate) in water. A higher zein number corresponds to a greaterdegree of irritation.

A 1% actives solution of each test surfactant (120 mL) is prepared. ThepH of each solution is adjusted to about 7.0 with dilute aq. sulfuricacid or dilute aq. sodium hydroxide. The surfactant solution is warmedto 45° C. Zein powder (1.50 g) is added to each of three jars.Surfactant (25.0 g of 1% actives solution) is added to each jar, and toone empty jar to be used as a blank. The solutions are mixed usingmagnetic stirring on a temperature-controlled hotplate at 45° C. for 60min. Each mixture is then centrifuged (2500 rpm, 15 min.), andundissolved zein powder is isolated by vacuum filtration. The residue iswashed with deionized water and dried (55° C., 24 h) to constant weight.The amount of undissolved zein protein is found gravimetrically, and theresults from three runs are averaged to give the % of solubilized zeinand zein number. Results appear in Table 1.

TABLE 1 Results of Zein Test¹ % solubilized zein zein number commentStepanol ® WA- 49.6 100 control Extra PCK (SLS) Unsat. C₁₁ alcohol 9.619.3 Unsaturated Na sulfate derivative is much Sat. C₁₁ alcohol 52.9 107less irritating than the Na sulfate saturated analog Unsat. C₁₁ alcohol8.3 16.7 Unsaturated 1EO Na sulfate derivative is much Sat. C₁₁ alcohol33.7 68.0 less irritating than the 1EO Na sulfate saturated analogUnsat. C₁₁ alcohol 16.5 31.6 Unsaturated 3EO Na sulfate derivative isless Sat. C₁₁ alcohol 22.3 44.9 irritating than the 3EO Na sulfatesaturated analog ¹Average of three runs

As shown in Table 1, the sulfate and ether sulfate derivatives made fromundecylenic alcohol are less or much less irritating than theirsaturated analogs based on the test results. All of the unsaturatedderivatives tested are far less irritating when compared with thecontrol, Stepanol® WA-Extra PCK (sodium lauryl sulfate). There appearsto be less of a difference in the zein number between the unsaturatedderivative and its saturated analog when the degree of ethoxylation isgreater.

Hard-Surface Cleaners: Glass Cleaner

Control: Stepanol WA-Extra® SLS (sodium lauryl sulfate, 1.0 g, productof Stepan, 29.4% active) is combined with isopropyl alcohol (2.0 g) anddiluted to 100 mL with deionized water.

Test Formulation: Test sample (1.2 to 1.4 g) is combined with isopropylalcohol (2.0 g) and diluted to 100 mL with deionized water.

Test Materials:

Saturated C₁₁ alcohol sulfate, Na salt, 21.2% actives

Unsaturated C₁₁ alcohol sulfate, Na salt, 27.4% actives

Saturated C₁₁ alcohol 3EO ethoxylate sulfate, Na salt, 25.5% actives

Unsaturated C₁₁ alcohol 3EO ethoxylate sulfate, Na salt, 25.4% actives

Formulations:

A: Saturated Na sulfate (1.4 g). Clear, pH 4-5

B: Unsaturated Na sulfate (1.1 g). Clear, pH 9-10

C: Saturated 3EO Na sulfate (1.2 g). Clear, pH 6-7

D: Unsaturated 3EO Na sulfate (1.2 g). Clear, pH 7-8

Method: The test formulation is evaluated for clarity; only clearformulations are evaluated in the low film/low streak test. The testmeasures the ability of the cleaner to leave a streak and film-freesurface on a test mirror. The test formula is applied to a mirror in acontrolled quantity and wiped with a standard substrate back and forth,leaving the spread product to dry. Once dry, the mirrors are evaluatedand rated by a two-person panel. Results appear in Table 2.

As shown in Table 2 (A versus B), the formulation based on the C₁₁unsaturated alcohol sulfate, sodium salt (formulation B) outperformsformulation A, which is based on a C₁₁ saturated alcohol sulfate, sodiumsalt in terms of a reduced degree of streaking.

Comparing formulations C and D, both the unsaturated alcohol 3EOsulfate, sodium salt, and its saturated analog perform similarly andwell in the test. Both perform nearly as well as the control in terms ofa low degree of filming and streaking and both perform better whencompared with the alcohol sulfate formulations (A & B).

TABLE 2 Glass Cleaner Performance Filming on Streaking on A versus BObservations mirror panel mirror panel Control Clear; no film or streak0% 0% B-Unsat. C₁₁ alcohol Slight streaking 0% 5% Na sulfate A-SaturatedC₁₁ alcohol Unacceptable 0% 30%  Na sulfate streaking Better of A and BB Filming on Streaking on C versus D Observations mirror panel mirrorpanel Control Clear; no film or streak 0% 0% D-Unsaturated C₁₁ Minimalspotting; 0% 1% alcohol 3EO Na sulfate almost equal to controlC-Saturated C₁₁ alcohol Very minor 0% 3% 3EO Na sulfatestreaking/spotting Better of C and D DHard Surface Cleaners: Aqueous Degreasers

This test measures the ability of a cleaning product to remove a greasydirt soil from a white vinyl tile. The test is automated and uses anindustry standard Gardner Straight Line Washability Apparatus. A cameraand controlled lighting are used to take a live video of the cleaningprocess. The machine uses a sponge wetted with a known amount of testproduct. As the machine wipes the sponge across the soiled tile, thevideo records the result, from which a cleaning percentage can bedetermined. A total of 10 strokes are made using test formulationdiluted 1:32 with water, and cleaning is calculated for each of strokes1-10 to provide a profile of the cleaning efficiency of the product.

Test Samples:

A neutral, dilutable all-purpose cleaner is prepared from propyleneglycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate(4.0 g), Bio-Soft® EC-690 ethoxylated alcohol (1.0 g, product ofStepan), test sample (1.1 to 1.4 g), and deionized water (to 100.0 gsolution). The control sample for anionic testing replaces the testsample with Stepanol® WA-Extra PCK (sodium lauryl sulfate, Stepan, 1.0g, 29.4% active).

Test Materials:

Saturated C₁₁ alcohol sulfate, Na salt, 21.2% actives

Unsaturated C₁₁ alcohol sulfate, Na salt, 27.4% actives

Saturated C₁₁ alcohol 3EO ethoxylate sulfate, Na salt, 25.5% actives

Unsaturated C₁₁ alcohol 3EO ethoxylate sulfate, Na salt, 25.4% actives

Formulations:

A: Saturated Na sulfate (1.4 g). Clear, pH 7.5

B: Unsaturated Na sulfate (1.1 g). Clear, pH 7.5

C: Saturated 3EO Na sulfate (1.2 g). Clear, pH 7.4

D: Unsaturated 3EO Na sulfate (1.2 g). Clear, pH 7.5

Soil Composition (from Gardner ASTM D4488-95 Method):

Tiles are soiled with a particulate medium (50 mg) and an oil medium (5drops). The particulate medium is composed of (in parts by weight)hyperhumus (39), paraffin oil (1), used motor oil (1.5), Portland cement(17.7), silica (18), molacca black (1.5), iron oxide (0.3), bandy blackclay (18), stearic acid (2), and oleic acid (2). The oil medium iscomposed of kerosene (12), Stoddard solvent (12), paraffin oil (1),SAE-10 motor oil (1), Crisco® shortening, product of J.M. Smucker Co.(1), olive oil (3), linoleic acid (3), and squalene (3).

Results appear in Table 3. As shown in the table, all of the testsamples perform equal to the control within the limits of the testmethod.

TABLE 3 Gardner Straight-Line Washability Test Ave. % clean after 2, 4,6, 8, or 10 swipes Rat- 2 4 6 8 10 ing WA-Extra (sat C₁₂ 91.3 93.6 93.294.1 95.4 control Na sulfate) Unsat C₁₁ alcohol 92.5 94.4 94.9 95.2 96.2equal Na sulfate Sat C₁₁ alcohol Na sulfate 91.4 94.5 96.4 98.2 97.5equal Unsat C₁₁ 3EO Na sulfate 94.0 97.4 99.1 96.5 100 equal Sat C₁₁ 3EONa sulfate 97.5 98.9 98.9 99.3 100 equalWater-Soluble Herbicide Formulation Testing

Surfactant candidates for water soluble herbicide applications areexamined as a replacement for the anionic, nonionic, or anionic/nonionicblend portion and compared to a known industry adjuvant standard for usein paraquat, a water soluble herbicide concentrate formulation. Astandard dilution test is conducted whereby the concentrates are dilutedin water to determine if solubility is complete.

Control: Paraquat (9.13 g of 43.8% active material) is added to a 20-mLglass vial. A known industry paraquat adjuvant (2.8 g) is added andvigorously mixed for 30 s. Deionized water (8.07 g) is added, and mixingresumes for 30 s. Standard 342 ppm water (47.5 mL) is added to a 50-mLNessler cylinder, which is stoppered and equilibrated in a 30° C. waterbath. Once the test water equilibrates, the formulated paraquat (2.5 mL)is added by pipette into the cylinder. The cylinder is stoppered andinverted ten times. Solubility is recorded as complete or incomplete.Cylinders are allowed to stand and the amount (in mL) and type ofseparation are recorded after 30 min., 1 h, 2 h, and 24 h. Results ofthe solubility testing appear in Table 4 below.

Anionic Test Sample: Paraquat (4.57 g of 43.8% active material) is addedto a 20-mL glass vial. An eight to ten mole alkyl phenol ethoxylatesurfactant (0.7 g) is added and vigorously mixed for 30 s. Test sample(0.7 g) is added and mixing resumes for 30 s. Deionized water (4.03 g)is added, and mixing resumes for 30 s. A 2.5-mL sample of the formulatedparaquat is added to 47.5 mL of 342 ppm hardness water, and testingcontinues as described above for the control sample.

Nonionic Test Sample: Paraquat (4.57 g of 43.8% active material) isadded to a 20-mL glass vial. Test sample (0.7 g) is added and vigorouslymixed for 30 s. Sodium linear alkylbenzene sulfonate (“NaLAS,” 0.7 g) isadded and mixing resumes for 30 s. Deionized water (4.03 g) is added,and mixing resumes for 30 s. A 2.5-mL sample of the formulated paraquatis added to 47.5 mL of 342 ppm hardness water, and testing continues asdescribed above for the control sample.

Adjuvant (Anionic/Nonionic) Test Sample: Paraquat (4.57 g of 43.8%active material) is added to a 20-mL glass vial. Test sample (1.4 g) isadded and vigorously mixed for 30 s. Deionized water (4.03 g) is added,and mixing resumes for 30 s. A 2.5-mL sample of the formulated paraquatis added to 47.5 mL of 342 ppm hardness water, and testing continues asdescribed above for the control sample.

Test Materials:

Saturated C₁₁ alcohol sulfate, Na salt, 21.2% actives

Unsaturated C₁₁ alcohol sulfate, Na salt, 27.4% actives

Saturated C₁₁ alcohol 1 EO ethoxylate sulfate, Na salt, 26.2% actives

Unsaturated C₁₁ alcohol 1EO ethoxylate sulfate, Na salt, 26.9% actives

Saturated C₁₁ alcohol 1 EO ethoxylate sulfate, NH₄ salt, 97.5% actives

Unsaturated C₁₁ alcohol 1EO ethoxylate sulfate, NH₄ salt, 95.5% actives

Saturated C₁₁ alcohol 3EO ethoxylate sulfate, Na salt, 25.5% actives

Unsaturated C₁₁ alcohol 3EO ethoxylate sulfate, Na salt, 25.4% actives

Criteria for emulsion solubility: Test samples should be as good as orbetter than the control with no separation after one hour. All of thetested formulations perform well in comparison to the controls,particularly when the saturated or unsaturated C₁₁ alcohol derivative isused to replace the anionic portion of the formulation (left set ofcolumns in Table 4). Overall, no significant difference is noted betweenthe unsaturated C₁₁ alcohol derivatives and their saturated counterpartsin this test. Results appear in Table 4.

TABLE 4 Water Soluble Herbicide Formulation: Emulsion stability, mLseparation Anionic Nonionic Adjuvant Rat- test sample sol 1 h 24 h sol 1h 24 h sol 1 h 24 h ing Unsaturated S 0 0 I 0.25 0.4 D 0 0.25 good Nasulfate Saturated S 0 0 I 0.2 0.3 I 0.2 0.4 good Na sulfate Unsat. 1EO S0 0 D 0.2 0.25 D 0 0.5 good Na sulfate Sat. 1EO S 0 0 D 0.2 0.5 D 0 0.2good Na sulfate Unsat. 3EO S 0 0 D 0.2 0.5 D 0 Tr good Na sulfate Sat.3EO S 0 0 D 0.1 0.5 D 0 Tr good Na sulfate Unsat. 1EO S 0 0 D 0 Tr S 0 0good NH₄ sulfate Sat. 1EO S 0 0 S 0 0 S 0 0 good NH₄ sulfate D =dispersable; S = soluble; I = insoluble; Tr = trace Control result:Solubility: D; 1 h: 0 mL; 24 h: 0.2Agricultural Dispersant Screening:

The potential of a composition for use as an agricultural dispersant isevaluated by its performance with five typical pesticide activeingredients: atrazine, chlorothalonil, diuron, imidacloprid andtebuconazole. The performance of each dispersant sample is evaluated incomparison with two standard Stepsperse® dispersants: DF-200 and DF-500(products of Stepan Company).

A screening sample is prepared as shown below for each active. Wettingagents, clays, and various additives are included or excluded from thescreening process as needed. The weight percent of pesticide (“technicalmaterial”) in the formulation depends on the desired active level of thefinal product. The active level chosen is similar to other products onthe market. If this is a new active ingredient, then the highest activelevel is used.

Samples are evaluated in waters of varying hardness, in this case 342ppm and 1000 ppm. The initial evaluations are performed at ambienttemperature. Other temperatures can be evaluated as desired. The 342 ppmwater is made by dissolving anhydrous calcium chloride (0.304 g) andmagnesium chloride hexahydrate (0.139 g) in deionized water and dilutingto 1 L. The 1000 ppm water is made similarly using 0.89 g of calciumchloride and 0.40 g of magnesium chloride hexahydrate.

Technical material (60-92.5 wt. %), anionic wetting agent (0.5-1.0 wt.%), silica (0.5-1.0 wt. %), and clay (balance) are blended in a suitablecontainer. The blend is milled to a particle size of at least a d(90) of<20μ using a hammer and air/jet mills as needed. Test dispersant (0.1 g)is added to test water (50 mL) in a beaker and stirred 1-2 min. Milledpowder containing the technical material (1.0 g) is added to thedispersant solution and stirred until all powder is wet (2-5 min.). Themixture is transferred to a 100-mL cylinder using additional test waterfor rinsing the beaker and is then diluted to volume. The cylinder isstoppered and inverted ten times, then allowed to stand. Visualinspection is performed at t=0.5, 1.0, 2.0, and 24 hours, and the amountof sediment observed (in mL) is recorded. Trace of sediment=“Tr” (seeTable 5).

Results appear in Table 5. As shown in the table, both the unsaturatedC₁₁ alcohol 1EO ethoxylate sulfate, sodium salt, and its saturatedanalog perform equal to the controls in this test.

TABLE 5 Agricultural Dispersants Testing: Anionic Wetting AgentSedimentation results at 1 h; 24 h (mL) test water, Unsaturated 1EOSaturated 1EO sodium ppm DF-200 DF-500 sodium sulfate sulfate Diuron 3421; 2 0.5; 1-1.5 0.5; 1   0.5; 1 1000 1; 2-2.5 0.5-0.75; 2 1, 2   1, 2(flock) Chlorothalonil 342 0.25; 1-1.25 0.25; 1-1.25 Tr.; 1 0.5; 1 10000.25-0.5; 1.25-1.5 2; 3 0.5; 1   0.5; 2 Imidacloprid 342 Tr; 1-1.50.5-1; 2 3, 4   1; 2 1000 Tr; 1-1.5 0.5-1; 2-2.5 3, 3 2.5, 2 (flock)Tebuconazole 342 Tr; 1.25 Tr; 1.5 Tr.; 2 Tr.; 0.5 1000 Tr; 3 Tr; 3flocked   5, 3 (flock) Atrazine 342 Tr-0.25; 1-1.5 0.5; 1   Tr.; 1 Tr.;1 1000 Tr-0.25; 1-1.5 6; 3 0.5; 1   0.5; 1 Rating control control equalequal

TABLE 6 Comparison of Monounsaturated C₁₁ Derivatives v. SaturatedAnalogs: Estimated Phase Region as a Function of % Actives Level¹Isotro- Solid/ Solid/ pic Lamel- Hexag- Cu- isotro- gum/ Clear lar onalbic pic paste Unsaturated 0-68 68-100 Na sulfate Saturated 0-33 33-4343-100 Na sulfate Unsat. 1EO 0-64 64-74 74-100 Na sulfate Sat. 1EO 0-3658-72 36-58 72-100 Na sulfate Unsat, 1EO 0-31 58-91 31-58 91-100 NH,sulfate Sat. 1EO 0-26 67-85 26-58 58-67 85-100 NH₄ sulfate Unsat, 3EO0-70 70-80 80-100 Na sulfate Sat. 3EO 0-33 58-82 33-58 82-100 Na sulfateUnsat. 7EO 0-38, 38-57 ethoxylate 57-98² Sat. 7EO 0-34, 63-78 34-63ethoxylate 78-98² ¹All microscopy examinations are performed at roomtemperature (20-22° C.). Phase boundaries are estimates. ²At ~98-100%actives, a two-phase liquid results.

Surfactant Phase Behavior Study:

Phase behavior is observed using an Olympus BH-2 cross-polarizedmicroscope at 100-400X and room temperature (20° C. to 22° C.). Themonounsaturated C₁₁ alcohol derivatives (sulfates, ethoxylate sulfates,and alcohol ethoxylates) are compared with their saturated analogs.

Samples are prepared by diluting the most concentrated product graduallywith deionized water. When the surfactant concentration approaches aphase transition, the concentration is varied at 2-4% intervals toestimate the phase boundary. The actives level reported in Table 6 foreach phase boundary is within ±5% of the true boundary.

Samples are loaded between a microscope slide and cover glass and areallowed to equilibrate before observation. Microscopic texture isanalyzed and used to determine the phase. For some samples, an AR 2000rheometer (TA Instruments) is used to measure viscosity at 25° C. tofurther verify phase behavior.

At low surfactant concentrations, randomly oriented micelles (spheres orcylinders) generally predominate, resulting in a clear or isotropicliquid. As concentration increases, cylindrical micelles can arrangethemselves into either hexagonal or cubic phases, both of which havevery high viscosities (10-50K cP at 25° C. for the hexagonal phase,higher for the cubic phase). Thus, in the hexagonal and cubic phases,the surfactant is difficult to process or formulate. Increasing thesurfactant concentration more can generate a lamellar phase, wheremicellar bilayers are separated by water. Because the lamellar phase ispumpable (1-15K cP at 25° C.), compositions having high levels ofsurfactant actives can be produced. Further concentration of thesurfactant can lead to reverse micelles, in some cases generating anisotropic mixture. In sum, phase behavior is important for manufacture,processing, transportation, and formulation of compositions containingsurfactants.

An ideal sample is isotropic and clear throughout the entire range ofactive levels with low viscosity, as this is most likely to avoid anyprocessing issues related with gelling or precipitation duringformulation. A lamellar phase is also considered favorable forprocessing and transportation. Less favorable gel phases include cubic,hexagonal, and solid/gum/paste. All of the samples tested had at leastsome gel/solid component. The presence of these phases at a particularactives level suggests that processing at or near that actives levelwill be very difficult.

As shown in Table 6, several of the unsaturated C₁₁ derivatives, notablythe alcohol sulfate sodium salts and alcohol ether sulfate sodium salts,have isotropic clear phases at actives levels from 0 to 60 or 70 wt. %.This suggests that these surfactants will have wide latitude forformulating at relatively high actives levels. When compared with theirsaturated analogs, the unsaturated C₁₁ derivatives unexpectedlydemonstrate favorable phase behavior (combination of isotropic clear andlamellar phases) over a much wider range of actives levels. The resultsindicate that the unsaturated derivatives will be easier to process thanthe saturated analogs in intermediate products or fully formulatedend-use applications.

Synergy Study: Combining Derivatives with Cationic Surfactant

The surfactant blends tested are prepared at a 1:1 molar ratio withoutany pH adjustment. Dilutions are made using deionized water to thedesired actives level. Actives amounts are wt. % unless indicatedotherwise. Appearances are reported at ambient temperature for samplesprepared within the last 24 h.

Interfacial tension (IFT) of all the individual components and theirblends is measured at 0.1 wt. % active against light mineral oil atambient temperature using a Kruss DSA-20 pendent drop tensiometer. Thedrop is blown out at 600 μL/min., and a video is recorded for 100 s. Thevideo frames taken during the last 15 s are analyzed and used for theIFT calculation.

For blends having an IFT less than 0.5 mN/m, the IFT is determined usinga spinning drop tensiometer (University of Texas 500) at 25° C. Oildensity=0.877 g/cm³ and surfactant density=0.997 g/cm³ are used for theIFT calculation.

The expected IFT for a blend is calculated based on ideal mixing(non-synergistic) using the active component in each blend. The equationused is given as:Expected IFT=X*IFTa+(1−X)*IFTbwhere X is the actives % of component A, IFTa is the IFT of component A,and IFTb is the IFT of component B. If the measured IFT for a blend isless than the expected IFT, then the blend is synergistic. If themeasured IFT for a blend is higher than the expected IFT, the system isantagonistic.

As shown in Table 7, the unsaturated C₁₁ alcohol sulfate, sodium salt,when combined with Ammonyx® Cetac 30, exhibits very high synergy andimproved solubility character compared with the saturated analog. Tables8-10 confirm that the solubility improvement from the unsaturatedderivatives is a general trend. Overall, the unsaturated derivativesdisplay a high level of synergy, i.e., as much or more than thesaturated analogs.

TABLE 7 Blends of Unsaturated or Saturated C₁₁ Na Sulfate with CationicSurfactants Sample Type anionic anionic cationic Name Unsat C₁₁ Na SatC₁₁ Na sulfate Ammonyx ® Cetac 30 sulfate (cetrimonium Cl)anionic:cationic (molar) 1:1 1:1 Appearance, 1.0% homogeneous, separatedclear liquid hazy liquid Appearance, 0.1% slightly hazy liquid separatedclear liquid IFT at 0.1% actives 5.95 16.34 0.35 (single component) IFTat 0.1% 0.17 2.67 actives/mineral oil (blend) Calculated IFT 3.16 8.35(no synergy) Synergy? very high above average Solubility good poor

TABLE 8 Blends of Unsaturated or Saturated C₁₁ 1EO Na Sulfate withCationic Surfactants Sample Type anionic anionic cationic Name Unsat.C₁₁ 1EO Sat. C₁₁ 1EO Ammonyx ® Na sulfate Na sulfate Cetac 30(cetrimonium Cl) anionic:cationic 1:1 1:1 (molar) Appearance, 1.0%separated separated clear liquid Appearance, 0.1% slightly hazy liquidhazy liquid clear liquid IFT at 0.1% actives 6.18 12.52 0.35 (singlecomponent) IFT at 0.1% 0.13 0.23 actives/mineral oil (blend) CalculatedIFT 3.27 6.44 (no synergy) Synergy? very high very high Solubility goodfair-poor

TABLE 9 Blends of Unsaturated or Saturated C₁₁ 1EO NH₄ Sulfate withCationic Surfactants Sample Type anionic anionic cationic Name Unsat.C₁₁ 1EO Sat. C₁₁ 1EO Ammonyx ® NH₄ sulfate NH₄ sulfate Cetac 30(cetrimonium Cl) anionic:cationic 1:1 1:1 (molar) Appearance, 1.0%homogeneous separated clear liquid hazy liquid Appearance, 0.1% slightlyhazy liquid hazy liquid clear liquid IFT at 0.1% actives 17.22 12.400.38 (single component) IFT at 0.1% 0.60 0.85 actives/mineral oil(blend) Calculated IFT 8.8 6.2 (no synergy) Synergy? very high highSolubility good fair-poor

TABLE 10 Blends of Unsaturated or Saturated C₁₁ 3EO Na Sulfate withCationic Surfactants Sample Type anionic anionic cationic Name Unsat.C₁₁ 3EO Sat. C₁₁ 3EO Ammonyx ® Na sulfate Na sulfate Cetac 30(cetrimonium Cl) anionic:cationic 1:1 1:1 (molar) Appearance, 1.0% hazyliquid separated clear liquid Appearance, 0.1% slightly hazy liquid hazyliquid clear liquid IFT at 0.1% actives 5.10 8.80 0.35 (singlecomponent) IFT at 0.1% 0.17 0.03 actives/mineral oil (blend) CalculatedIFT 2.73 4.58 (no synergy) Synergy? high very high Solubility goodfair-poor

The preceding examples are meant only as illustrations; the followingclaims define the invention.

We claim:
 1. A process which comprises reacting a composition comprisinga monounsaturated C₁₀-C₁₂ alcohol with an alkoxylating agent, asulfating agent, or an alkoxylating agent followed by a sulfating agentto make, respectively, an alkoxylate, a sulfate, or an ether sulfate. 2.The process of claim 1 wherein the monounsaturated C₁₀-C₁₂ alcohol oralkoxylate is reacted with sulfur trioxide in a falling-film reactor,followed by neutralization.
 3. A process for making an internallymonounsaturated C₁₀-C₁₂ alcohol sulfate or ether sulfate, the processcomprising reacting a terminally monounsaturated C₁₀-C₁₂ alcohol oralkoxylate with sulfur trioxide in a falling-film reactor, followed byneutralization.
 4. A composition comprising water and 1 to 99 wt. % of asurfactant, wherein the surfactant comprises an ether sulfate of theformula:CH_(2═)CH—(CH₂)₉—O—(EO)_(n)—SO₄ ⁻M⁼ wherein n is the average number ofEO units and has a value from 1 to 5, and M is Na, K, Li, or NH₄.
 5. Thecomposition of claim 4 wherein M is Na or NH₄.
 6. The composition ofclaim 4 wherein M is Na and n is 1 or
 3. 7. The composition of claim 4wherein M is NH₄ and n is
 1. 8. A composition comprising water and 1 to99 wt. % of a surfactant comprising sulfates of undecylenic alcohol,wherein the surfactant comprises: (a) 40 to 60 wt. % of amonounsaturated C₁₁ primary alcohol sulfate; and (b) 40 to 60 wt. % of asecondary hydroxyalkyl C₁₁ primary alcohol sulfate.
 9. The compositionof claim 8 comprising 2 to 98 wt. % of the surfactant.
 10. Thecomposition of claim 8 wherein the surfactant further comprises 0.1 to20 wt. % of sulfonated products.
 11. The composition of claim 8 made bysulfating undecylenic alcohol with sulfur trioxide in a falling-filmreactor, followed by neutralization.